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By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By J. W. Downey, R. A. Morris, M. V. Nevitt

An experimental survey has determined the occurrence of Ti2 Ni-type phases in binary and ternary alloys of Ti, Zr, or Hf with first, second, or third long-period transition metals and also in ternary systems in which 0 is the third component. The existence of eleven previously unreported isomorphs is cited and some approximate phase boundaries are given. Lattice parameters are reported for the new phases. The periodic table relationships involved in the occurrence of the phase are discussed. A previous paper' reported the occurrence of a group of Ti2Ni-type phases (structure-type E93) containing Zr in combination with Rh, Ir, and Pt, and Hf in combination with Rh, Pd, Ir, and Pt, and cited evidence to show that all of the Zr phases and the Hf-Pd phase are not binary phases but occur only when 0 is present. More recently one of the present authors found that in the ternary systems of Ti and 0 with Cr, Mn, Fe, Co, and Ni the occurrence of the Ti2Ni-type phase could be correlated qualitatively with valency electron concentration, and that the role of 0 appeared to be that of an electron acceptor.' This paper describes the results of a broader investigation of the occurrence of Ti2Ni-type phases in binary and ternary systems containing Ti, Zr, or Hf. EXPERIMENTAL PROCEDURE Alloys were prepared by arc melting. The purity of the metals Zr, Rh, Hf, Ir, Pd, and Pt was given in the previous paper.' The additional materials used for this work were metals with a minimum purity of 99.9 pct and reagent grade ZrO2, TiO2, Cr2O3, and NiO. Chemical analysis of several alloys in each system indicated good agreement between intended compositions and cast-button compositions. For the heat treatment precautions were taken to avoid oxygen contamination. The specimens were wrapped in Mo foil and sealed in fused quartz tubes at a room temperature pressure of 1 x mm of Hg. These capsules were then annealed in a vacuum furnace at an external pressure of 5 X mm of Hg. Since the major constituent in most of the alloys studied was the brittle Ti2Ni-type phase, Debye-Scherrer patterns with sharp lines could be obtained with powder crushed from the annealed solid samples without being reannealed. Metallographic, X-ray diffraction, and density determination techniques previously described1, 2 were used. RESULTS AND DISCUSSION Zr-Rh-O, Zr-Ir-Oand Zr-Pt-O Systems-Figs. 1 through 3 show the approximate boundaries of the Ti2Ni-type phase fields at the temperatures indicated in the ternary systems Zr-Rh-O, Zr-Ir-O and Zr-Pt-0. In each isothermal section the Ti2Ni-type phase field is labeled E and the unidentified binary phase found in the previous work' is labeled ?. The dotted lines, which are not phase boundaries, correspond to the composition (Zr2 B)1-xOx. In each system the Ti2Ni-type phase field is displaced to the high-Zr side of this composition line. However, the departures from Zr2B stoichiometry for the metal components are not as high as Zr3B, as was inferred from the previous work. Lattice parameters of the Ti2Ni-type phases in the alloys shown as triangular data points in Figs. 1 through 3 are given in Table IA. The probable compositions of the Ti2Ni-type phases have been estimated from the isothermal sections. Although there are a few exceptions that probably result from uncertainties in phase boundary location and from the effect of variation of oxygen content, the generalization can be

Jan 1, 1961

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934

By Robert Ammon

The milling practice at Mascot, at present, consists of dry crushing to % in., jigging, fine grinding, and flotation. The ore arrives at the mill from two mines, No. 1 mine shaft being located in the mill proper, and No. 2 mine shaft being situated about 2000 ft. east of the mill. No. 2 mine is served by a coarse-crushing plant and aerial tramway to the mill bins. In jigging the No. 2 mine ore, 50 per cent. of the mill feed is rejected by the jigs as a jig tailing ranging from 5/8 in. to 10 mesh; the balance of this ore, after removing a jig concentrate, is ground to flotation feed. In jigging No. 1 mine ore, approximately 80 per cent. of the mill feed is rejected as a coarse jig tailing, and the balance is ground to flotation feed without the removal of a jig concentrate. The difference in the treatment is due to the fact that No. 2 mine ore carries a higher content of zinc than that from No. 1 mine. Of the total concentrates produced, 30 per cent. is made on jigs and 70 per cent. by flotation. At present, 1350 tons of No. 2 ore and 800 tons of No. 1 ore are treated each 24 hours. The recoveries for a typical week are as follows: Heads.......................... 3.55 Jig concentrates................ 61.30 Jig tails......................... 0.80 Flotation concentrates........... 60.60 Flotation tails................... 0.09 Extraction..................... 86.50 The associated minerals are a straw-colored sphalerite, dolomite, calcite, pyrite, quartz, and a small amount of greenockite, which occurs as a stain and sometimes small crystals along with sphalerite, but is comparatively rare. Pyrite is present in small quantities, usually less than 0.5 per cent.; quartz occurs in bands a few inches thick. A complete analysis of the ore is as follows: PEr Cent. Per Cent. Calcium carbonate.............. 48.11 Zinc sulfide.................... 5.43 Magnesium carbonate........... 35.36 Cadmium sulfide............... Nil Silica.......................... 8.73 Lead sulfide................... Nil Alumina....................... 1.04 Iron oxide...................... 1.33 Total....................... 100.00

Jan 1, 1925

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By Joseph Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned.

Jan 1, 1929

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

By J. Ruzicka

IN creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently bear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addi-tion to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabri-cated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment.

Jan 1, 1937

By J. B. Chatelain, M. F. Dufour

FLUID jet mills, employing a compressible fluid to grind materials to the subsieve range, was developed in the early 1930's, and the subsequent acceptance of these units was the result of their ability to pulverize solids that, because of physical properties, could not be processed by other attrition methods, such as ball, pebble, and hammer mills. Also, the fluid energy pulverizer is the only grinding device that will discharge continuously a 5-micron or smaller product. Simultaneous ultra-fine grinding and classification is the widest application of this unit. Jet mills may be used to advantage to reduce particle size of solids suspended in liquids, for coating one material with another, and effecting chemical reactions and changes in physical characteristics other than a reduction in size. Materials that can be processed by this grinding method include nonmetallic and metallic minerals, ores, metals, pigments, insecticides, fungicides, pharmaceuticals, plastics, dyes, and numerous other organic and inorganic products. Grinding principles utilized in the fluid mills available on the market are basically the same, the major difference being in the shape of the, grinding and classification chamber. Grinding in fluid jet pulverizers is accomplished by collisions between particles of the material being ground with the energy being supplied by compressed fluids entering the grinding chamber at high velocities. The "Micronizer" is a fluid energy mill employing a relatively flat cylindrical grinding chamber. Fig. 1 shows general construction details. The mill shown is equipped with a venturi type feeder using a compressed fluid to inject the feed into the grinding chamber. The energy consumed in forcing the feed into the grinding chamber against the mill pressure is, in some cases, as much as 40 pct of the total required for processing. Recent improvements, using a compression screw feeder as shown in Fig. 2, can reduce this to 1 or 2 pct of the total energy requirements. Grinding Grinding, as carried out in the. Micronizer involves the action of gaseous jets emerging from nozzles located in the peripheral wall of the grinding chamber. The axes, of the jets are tangential to a circle of smaller diameter than the grinding chamber as is shown in Fig. 1, and the gases entering the chamber maintain a high rotational velocity. The feed introduced into the mill is accelerated by the rotating gases and is thrown to the outside where a portion, coming in the zone of action of a nozzle, is further accelerated tangentially and inward. Violent collisions occur between the particles so accelerated and other particles circulating at a slower rate in a thin band near the periphery. It is estimated over 90 pct of the reduction in Micronizers occur as a result of impact within a fraction of an inch of the orifice. Observations also indicate that size reduction is independent of any interaction with the walls of the

Jan 1, 1952

By Chas. H. Behre, Arbiter. Nathaniel

Two outstanding factors characterize most undertakings in the mineral industries: (1) mineral deposits are not equally distributed over the earth but are localized by natural processes, and (2) the mineral industries are largely based upon wasting assets. Neither of these factors is invariably true, for a few mineral materials, such as water, are essentially world-wide and others are replaced periodically by processes not unlike crop production. Indeed, with some, such as the salts in the sea, the supply is cyclic in short or long periods, whereas others, like water, though locally or periodically in short supply, are essentially inexhaustible. But to the extent that most minerals are limited to certain areas and are "permanently" consumed, any industry founded upon them, by implication, demands great care in planning for the most effective extraction-the essence of wise and conservative expenditure. Several less unusual yet also truly fundamental factors in the economics of the mineral industry are those involving (1) the various kinds and properties of mineral materials, which influence their use; (2) their geo- logic and geographic availability; and (3) the techniques unique to their discovery, exploration, and utilization. This chapter is designed primarily as a brief background for later ones and as a summary of the several un- usual or at least special factors and of their effect upon the economics of the mineral industry. The social and political and especially the economic aspects of the industry are the main subjects of this volume and are dealt with in extended fashion in subsequent chapters. Fundamental Characteristics of Mineral Deposits DEFINITIONS Minerals are naturally occurring compounds of nonliving matter, each technically defined as having (1) a chemical composition that may vary

Jan 1, 1959

By E. S. Wheeler, M. W. Murphy

A LARGE part of the molybdenum produced in Colorado is converted and consumed in the Eastern States. As the raw materials and the power needed for the conversion of the Colorado concentrate are also accessible in the Eastern States, the conversion plant has been installed some 1500 miles east of where the ore is mined and milled. When concentrate was first produced at Climax in 1918, a custom smelter converted the product into ferromolybdenum. By 1924, the Company had decided to produce calcium molybdate and rented a building and installed equipment for that purpose at Langeloth, near Burgettstown, Pa., about thirty miles west of Pittsburgh. For the first few years the plant was a simple one of small capacity. A small hand-rabbled roaster was used, the product of which was made iota calcium molybdate by a conventional method; then an eight hearth mechanically rabbled roaster was installed to increase and speed up production. The output was considerably less than a million pounds of contained molybdenum annually until 1928, when a small part of the produc-

Jan 1, 1946

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By J. B. Conway

RECENT studies of first-stage creep data have led to a special least-squares procedure for use in calculating the Andrade creep-equation constants. This procedure is easy to apply, uses only experimental data, and yields results which do not vary with the individual making the analysis. Taking logarithms of the Andrade equation I = lo(1 +ßl1/3)ekt leads to In l = In lo + In(1 + ßl1/3) + kt A residual can then be defined as the difference between the logarithm of an experimental length value and the logarithm of a calculated length value. Following the usual least-squares approach differentiation with respect to 10 and k of the expression for the sum of the squares of the residuals leads to two equations which cannot be solved directly for the three constants involved. However, values of ß can be assumed and corresponding values of lo and k can then be calculated. Then the sum of the squares of the residuals can be calculated. For a certain value of ß this sum will exhibit a minimum value to identify the least-squares values for ß, lo, and k. An illustration of the application of the above least-squares approach is obtained by employing the creep data for lead originally presented by Andrade' in the development of the one-third creep law. A plot of the sum of the squares of the residuals as a function of ß is shown in Fig. 1 along with the corresponding lo and k values. The minimum is seen to occur at ß = 0.0143 from which lo = 39.149 and k = 7.27 x 10-5. Based on these results the Andrade equation for these lead data is 1 = 39.149(1 + 0.0143 t1/3)e7.27 x 10-5t compared to the equation I = 39.13(1 + 0.01457/l/3)e6.95 X 10-5t developed by Andrade (calculation procedure not given but was probably a graphical solution). Calculating length values using the above equations and comparing with the experimental length values, residuals corresponding to the difference between experimental and calculated length values can be obtained. The sum of the squares of the residuals can then be calculated. For the case of the least-squares approach a value for this sum was found to be 2.37 x 10-3 compared to a value of 3.47 x 10" for the equation originally proposed by Andrade. In other words, while the constants proposed by Andrade provide an excellent fit for the lead data, a still better representation is afforded by applying the least-squares approach discussed above. A similar result was obtained for the lead data at 162oc.l The least-squares approach led to 1 = 9.866(1 + 0.0497 t1/3)el.011 x 10-2t compared to the equation I = 9.94(1 + 0.0433 l1/3)e1.06 X 10-2t given by Andrade. In this case, too, the sum of the squares of the residuals is slightly smaller for the equation based on the least-squares approach. It should be pointed out that a double trial and er-

Jan 1, 1965

E. DEGOLYER,-New York, N. Y. (written discussion*).-Since the eastern part of the Gulf Coastal Plain is receiving considerable attention from various operators at the present time, it occurs to me that it brief review of most recent operations may be of interest in this connection, as well as a discussion of some of the points suggested by Mr. Hager. During the latter part of January, 1918, the Alahoma Oil Co. completed and abandoned a 3400-ft. (1036-m.) dry hole in Section 25, Township-8 North, Range 1 West. This well was drilled near the axis of the

Jan 4, 1918

By H. G. Moulton

The increasing scale of mining operations over the past decade, particularly in connection with the exploitation of large bodies of comparatively low-grade copper ores, has made necessary the study of the behavior of rock under failure. When extractions of as high as 40,000 tons a day are reached in steam-shovel operations and as high as 20,000 tons per day in underground mining operations, it is evident that excavations soon become of such size that the behavior of the rock will often be dependent on fundamental principles applicable to more or less homogeneous materials under stress, rather than on weathering or local planes of weakness. In the ordinary rock excavations encountered in civil-engineering practice, such as excavations for subways, highways, railroads, etc., rock faces are not carried to depths sufficient to develop any pressures, or consequently any failures, except those due to loose masses resulting from local planes of weakness. When, however, orebodies whose tonnage is measured by hundreds of thousands are to be extracted by steam-shovel operations in open pits, it is necessary to determine if possible in advance the slopes that the sides of the pits will assume, for these slopes influence the shape of the excavations and thereby the amount of ore that may be extracted by the open-pit method. When large orebodies are mined underground at depths of 300 to 500 ft. (91 to 152 m.) by caving methods, the surface subsiding as the ore is withdrawn, it is necessary to determine in advance the outermost limits of fracture in the subsiding surface, for on the delineation of these limits depends the location of surface improvements, mills, smelters, etc. and also the location of development work, such as hoisting shafts, main haulage levels, and all other underground openings that must remain undisturbed during the period of ore extraction. Heretofore, in civil-engineering practice, it has been assumed that earth and rock behave differently in failure. For the calculation of earth pressures, formulas are used in which the assumption is made that earth banks fail by sliding along the slope determined by the frictional resistance of the material. The line of failure and the resulting pressure is held to be dependent on the angle of repose, which is different for varying

Jan 1, 1920

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By F. W. Schroeder

AT the annual meeting of the Institute 2 years ago, a paper,1 " Requirements of Refractories for Open Hearths," was presented by F. W. Davis and G. A. Bole of the U. S. Bureau of Mines. In a brief foreword, D. A. Lyon stated that the paper was not to report the results obtained but rather to present an outline to serve as a basis for discussion. The essential parts of an open-hearth furnace were described and the conditions under which they operate. Some constructive discussion followed the reading of the paper. One of the first fellowship investigations undertaken by the Bureau of Mines in 1924 under the cooperative agreement with Carnegie Institute of Technology, through the Metallurgical Advisory Board, was to determine service conditions of open-hearth refractories. The present paper gives the results of this work which was done in the Pittsburgh district and was in charge of the authors. Material contributions in the form of data were contributed by E. N. Bauer, J. W. Campbell, G. H. Pfeiffer and A. Grodner, Carnegie Institute of Technology research fellows. The study covered 18 mos.

Jan 7, 1926

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968